1. Field of the Invention
This invention relates to carboxyl radical containing resin hair setting or hairspray compositions possessing improved adhesion to the hair which are more readily removed from the hair due to the use of certain long chain amine-functional neutralizing agents containing a hydrophilic radical in addition to the amine radical as well as a long chain hydrocarbon radical. Such neutralizing agents also improve the compatibility of hairspray resins with hydrocarbon propellants.
2. Description of the Prior Art
Hair setting and hairspray resins are generally based on the use of polymers which are inherently water soluble such as those based on polyvinylpyrrolidone and those which are generally hydrophobic, but are rendered water soluble by virtue of the presence of pendant groups such as carboxyl radicals.
In the latter case, the polymers are rendered water soluble of water dispersible by neutralizing the carboxyl radicals to form a water soluble ammonium complex (e.g., using ammonium hydroxide) or an amine complex (e.g., using 2-amino-2-methyl-1-propanol also known as "aminomethyl propanol"). Examples of neutralizing agents are given in U.S. Pat. Nos. 2,996,471 to Reiter et al. and 4,192,861 to Micchelli et al. The number of such pendant radicals and the percentage of the same which are neutralized determines the solubility in water and hydrophilic solvents such as ethanol which are commonly used as solvents in hairsprays for reasons of nontoxicity and lack of disagreeable odor.
The degree of neutralization is generally balanced against the reduction of hydrophilicity caused by such neutralization. The remainder of the polymer is typically hydrophobic to provide desired dry film characteristics and also compatibility with solvents and any aerosol propellants that may be used to deliver the hairspray resin to the hair. Too much neutralization may result in moisture sensitive films which tend to become tacky and may result in separation of the polymer from the solvent and/or propellant in the container due to loss of the hydrophobic character of the resin that provides hydrocarbon compatibility. Some hairspray resins such as those based on acrylic acid or methacryclic acid as the source of carboxyl radicals along with more hydrophobic alkyl acrylates and/or alkyl methacrylates are not as soluble as formulators desire in the hydrocarbon propellants now favored over fluorocarbon propellants for ecological reasons.
U.S. Pat. No. 4,192,861 to Micchelli et al. addresses the problem of reduced hydrocarbon compatibility in neutralized hairspray resins derived from copolymers of unsaturated monocarboxylic acids and vinyl or vinylidene monomers by neutralizing at least 50% of the carboxyl radicals desired to be neutralized with specific long chain amines. The amines taught as being useful for this purpose are primary, secondary or tertiary long chain amines wherein the long chain amines contain 8 to 20 carbon atoms and preferably 12-18 carbon atoms such as actadecyl amine, octyl amine, hexadecyl amine, and stearyl amine. None of the long chain amines taught contain any functional groups other than the amine radical. The minor remaining amount of the neutralizing agent can optionally be conventional amines used to neutralize hairspray resins such as aminomethyl propanol. This provides a simple method to increase the hydrocarbon compatibility of the hairspray resin. However, it can decrease the water solubility of the resin since the only functional group present is the amine group which complexes with the carboxyl radical of the resin leaving the hydrophobic tail portion of the amine extending away from the complex.
British Pat. No. 1,321,836 to Wilson has a disclosure similar to that of the Micchelli et al. Patent. It teaches improving the aerosol propellant (halogenated hydrocarbons are preferred) compatibility of hairspray resins based on unsaturated dicarboxylic acids such as maleic acid and a vinyl or vinylidene monomer which have been partially esterified by reacting from 5-20% of the remaining carboxyl groups with a primary amine containing from 4 to 16 carbon atoms. The only amines taught contain a single hydrocarbon radical in addition. to the --NH.sub.2 radical. An additional number of carboxyl radicals can be neutralized with conventional neutralizing agents such as aminomethyl propanol.
U.S. Pat. No. 2,996,471 to Reiter et al. teaches improving the water solubility of a copolymer of vinyl acetate and crotonic acid for use in hairspray applications by reacting the carboxyl groups present with amino alcohols such as aminomethyl propanol or 2-amino-1-phenyl-1-butanol.
Another example of a method by which the characteristics of resins based on N-vinylpyrrolidone monomer can be modified is found in U.S. Pat. No. 3,728,319 to Kiesel et al. It teaches reacting a preformed polymer of N-vinylpyrrolidone or copolymers of that monomer with other unsaturated monomers with secondary or tertiary amines having alkyl groups of 1 to 50 carbons to produce an amino-alkylated polymer that is useful as an electrostatic toner dispersant or intermediate for making quaternized polymers or polymers containing amine oxide radicals. The amine must be reacted with the N-vinylpyrrolidone radicals in the polymer using a free radical catalyst.
On pages 6 and 7, National Starch and Chemical Corporation Specialty Chemicals Bulletin "Technical Information: AMPHOMER.RTM." (12182 Supercedes 12280) teaches the use of MONAMID 716 (Lauramide DEA) from Mona Industries in various hairsprays containing AMPHOMER resin which is a carboxylated acrylic hairspray resin that is further described infra. However, the MONAMID 716 appears to be added as a hair conditioner since the amide radical in the Lauramide DEA (diethanolamide) does not function as a neutralizing agent.